Pyridine derivatives as fungicidal compounds

ABSTRACT

Compound of general formula (I): Process for preparing this compound. Novel intermediate of general formula (E): for the preparation of compound of general formula (I) Fungicidal composition comprising a compound of general formula (I). Method for treating plants by applying a compound of general formula (I) or a composition comprising it.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a 35 U.S.C. §371 national phase conversion of International Application No. PCT/EP2004/002381 filed Feb. 12, 2004, which claims priority of European Application No. 03356029.3 filed Feb. 19, 2003.

The present invention relates to novel N-[2-(2-pyridinyl)ethyl]carboxamides derivatives, their process of preparation, their use as fungicides, particularly in the form of fungicidal compositions, and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

The international patent application WO 01/11965 discloses a broad family of fungicidal compounds which generically covers the compounds according to the present invention. Nevertheless, the compounds according to the present invention are not specifically disclosed in this document and their activity as fungicides has not been tested.

It is always of high-interest in agriculture to use pesticidal compounds more active than the compounds already known by the man ordinary skilled in the art in order to decrease the quantity of active ingredient used by the farmer as to maintain an efficacy at least equivalent to compounds already known.

We have now found a new family of compounds selected in a broad family of compounds which possess the above mentioned characteristics.

Accordingly, the present invention relates to N-[2-(2-pyridinyl)ethyl]carboxamide derivative of general formula (I):

in which:

-   -   X may be an oxygen atom or a sulphur atom;     -   Y may be the same or different and may be a halogen atom, a         nitro group, a cyano group, a hydroxy, a carboxzyl group, a         C₁-C₈-alkyl, a C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms,         a C₁-C₈-alkylamino, a di-C₁-C₈-alkylamino, a C₁-C₈-alkoxy, a         C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, a         C₁-C₈-alkylthio, a C₁-C₆-halogenoalkylthio having 1 to 5 halogen         atoms, a C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1         to 5 halogen atoms, a C₃-C₈-alkinyloxy, a         C₃-C₈-halogenoalkinyloxy having 1 to 5 halogen atoms, a         C₃-C₈-cycloalkyl, a C₁-C₈-alkoxycarbonyl, a         C₁-C₈-alkylsulphinyl, a C₁-C₈-alkylsulphonyl, a         C₁-C₈-halo-genoalkylsulphinyl having 1 to 5 halogen atoms, a         C₁-C₈-halogenoalkylsulphonyl having 1 to 5 halogen atoms or a         C₁-C₆-alkoximino-C₁-C₆-alkyl;     -   R¹ may be a hydrogen atom, a cyano group, a nitro group, a         formyl group, a C₁-C₆-alkyl, a C₁-C₆-alkylcarbamoyl, a         C₂-C₆-alkenyl, a C₂-C₆-alkynyl, a C₁-C₆-halogenoalkyl having 1         to 7 halogen atoms, a C₁-C₆-alkoxy-C₁-C₆-alkyl, a         C₁-C₆-cyanalkyl, a C₁-C₆-aminoalkyl, a C₃-C₆-cycloalkyl, a         C₁-C₆-alkylcarbonyl, a C₁-C₆-halogenalkylcarbonyl having 1 to 5         halogen atoms, a C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl, a         C₁-C₆-alkylsulfanyl or a C₁-C₆-halogenalkylsulfanyl having 1 to         5 halogen atoms;     -   n maybe 1, 2, 3 or 4; and     -   Het represents an optionally substituted 5-, 6- or 7-membered         non-fused heterocycle with one, two or three heteroatoms which         may be the same or different; Het being linked by a carbon atom.

In the context of the present invention:

-   -   halogen means fluorine, bromine, chlorine or iodine;     -   heteroatom means N, O or S.

According to the present invention, X represents an oxygen atom or a sulphur atom. Preferably, X represents an oxygen atom.

According to the present invention, the 2-pyridyl may be substituted in every position by (Y)_(n), in which Y and n are as defined above. Preferably, the present invention relates to N-[2-(2-pyridinyl)ethyl]carboxamide derivative of general formula (I) in which the different characteristics may be chosen alone or in combination as being:

-   -   as regards n, n is 1 or 2. More preferably n is 2.     -   as regards Y, at least one of the Y substituent is a halogen         atom, a C₁-C₈-alkyl, a C₁-C₆-halogenoalkyl having 1 to 5 halogen         atoms or a C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl. More preferably, at         least one of the Y substituent is a C₁-C₆-halogenoalkyl having 1         to 5 halogen atoms. Even more preferably, at least one of the Y         substituent is —CF₃.     -   as regards the positions in which the 2-pyridyl is substituted,         the 2-pyridyl is substituted in 3- and/or in 5-position.

Even more preferably, the substituent in 5-position is —CF₃.

According to the present invention, “Het” of the compound of general formula (I) may be a five membered ring non-fused heterocycle. Specific examples of compounds of the present invention where Het is a five membered heterocycle include:

-   -   Het represents a heterocycle of the general formula (II)

-   -    in which:         -   R² and R³ may be the same or different and may be a hydrogen             atom, a halogen atom, an amino group, a nitro group, a             C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5 halogen             atoms; and         -   R⁴ may be a hydrogen atom, a halogen atom, a nitro group, a             C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5 halogen             atoms.     -   Het represents a heterocycle of the general formula (III)

-   -    in which:         -   R⁵ may be a hydrogen atom, a halogen atom, a C₁-C₄-alkyl or             a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and         -   R⁶ and R7⁶ may be the same or different and may be a             hydrogen atom, a halogen atom, an amino group, a C₁-C₄-alkyl             or a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (IV)

-   -    in which:         -   R⁸ may be a halogen atom, a C₁-C₄-alkyl or a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and     -   R⁹ may be a hydrogen atom, a C₁-C₄-alkyl or a         C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (V)

-   -    in which:         -   R¹⁰ and R¹¹ may be the same or different and may be a             hydrogen atom, a halogen atom, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a             C₁-C₄-alkylthio, a C₁-C₄-alkylsulphonyl, a phenyl optionally             substituted by a halogen atom or a C₁-C₄-alkyl or a pyridyl             optionally substituted by a halogen atom or a C₁-C₄-alkyl;             and     -   R¹² may be a hydrogen atom, a halogen atom, a cyano group, a         C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms         or a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (VI)

-   -    in which:         -   R¹³ and R¹⁴ may be the same or different and may be a             hydrogen atom, a halogen atom, a C₁-C₄-alkyl, a             C₁-C₄-alkyloxy or a C₁-C₄-halogenoalkyl having 1 to 5             halogen atoms; and     -   R¹⁵ may be a hydrogen atom, a halogen atom, a C₁-C₄-alkyl or a         C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (VII)

-   -    in which:         -   R¹⁶ may be a hydrogen atom, a halogen atom, a cyano group, a             C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5 halogen             atoms;         -   R¹⁷ and R¹⁹ may be the same or different and may be a             hydrogen atom, a halogen atom, a C₁-C₄-alkyl or a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and         -   R¹⁸ may be a hydrogen atom, a cyano group, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a             C₁-C₄-alkoxy-C₁-C₄-alkyl, a hydroxy-C₁-C₄-alkyl, a             C₁-C₄-alkylsulphonyl, a di(C₁-C₄-alkyl)aminosulphonyl, a             C₁-C₆-alkylcarbonyl, a phenylsulphonyl optionally             substituted by a halogen atom or a C₁-C₄-alkyl, or a benzoyl             optionally substituted by a halogen atom or a C₁-C₄-alkyl.     -   Het represents a heterocycle of the general formula (VIII)

-   -    in which:         -   R²⁰ may be a hydrogen atom, a cyano group, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a             C₁-C₄-alkoxy-C₁-C₄-alkyl, a hydroxy-C₁-C₄-alkyl, a             C₁-C₄-alkylsulphonyl, a di(C₁-C₄-alkyl)aminosulphonyl, a             C₁-C₆-alkylcarbonyl, a phenylsulphonyl optionally             substituted by a halogen atom or a C₁-C₄-alkyl, or a benzoyl             optionally substituted by a halogen atom or a C₁-C₄-alkyl;             and         -   R²¹, R²² and R²³ may be the same or different and may be a             hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl,             a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms or a             C₁-C₄-alkylcarbonyl.     -   Het represents a heterocycle of the general formula (IX)

-   -    in which:         -   R²⁴ may be a hydrogen atom or a C₁-C₄-alkyl; and         -   R²⁵ may be a halogen atom, a C₁-C₄-alkyl or a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (X)

-   -    in which:         -   R²⁶ may be a hydrogen atom or a C₁-C₄-alkyl; and     -   R²⁷ may be a halogen atom, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl         having 1 to 5 halogen atoms or a phenyl optionally substituted         by a halogen atom or a C₁-C₄-alkyl.     -   Het represents a heterocycle of the general formula (XI)

-   -    in which:         -   R²⁸ may be a hydrogen atom, a halogen atom, an amino group,             a cyano group, a C₁-C₄-alkylamino, a di-(C₁-C₄-alkyl)amino,             a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen             atoms or a phenyl optionally substituted by a halogen atom             or a C₁-C₄-alkyl; and     -   R²⁹ may be a halogen atom, a C₁-C₄-alkyl or a         C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (XII)

-   -    in which:         -   R³⁰ may be a hydrogen atom, a halogen atom, an amino group,             a cyano group, a C₁-C₄-alkylamino, a di-(C₁-C₄-alkyl)amino,             a C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5 halogen             atoms; and         -   R³¹ may be a halogen atom, a C₁-C₄-alkyl or a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (XIII)

-   -    in which:         -   R³² may be a hydrogen atom, a halogen atom, a cyano group, a             nitro group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1             to 5 halogen atoms, a C₃-C₆-cycloalkyl, a C₁-C₄-alkoxy, a             C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a             C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5             halogen atoms, an aminocarbonyl group or an             aminocarbonyl-C₁-C₄-alkyl;         -   R³³ may be a hydrogen atom, a halogen atom, a cyano group, a             nitro group, a C₁-C₄-alkyl, a C₁-C₄-alkoxy or a             C₁-C₄-alkylthio; and         -   R³⁴ may be a hydrogen atom, a phenyl, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a             hydroxy-C₁-C₄-alkyl, a C₂-C₆-alkenyl, a C₃-C₆-cycloalkyl, a             C₁-C₄-alkylthio-C₁-C₄-alkyl, a C_(1-C)             ₄-halogenoalkylthio-C₁-C₄-alkyl having 1 to 5 halogen atoms,             a C₁-C₄-alkoxy-C₁-C₄-alkyl or a             C₁-C₄-halogenoalkoxy-C₁-C₄-alkyl having 1 to 5 halogen             atoms.     -   Het represents a heterocycle of the general formula (XIV)

-   -    in which:         -   R³⁵ may be a hydrogen atom, a halogen atom, a cyano group, a             nitro group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1             to 5 halogen atoms, a C₃-C₆-cycloalkyl, a C₁-C₄-alkoxy, a             C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a             C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5             halogen atoms, an aminocarbonyl or an             aminocarbonyl-C₁-C₄-alkyl;         -   R³⁶ may be a hydrogen atom, a halogen atom, a cyano group, a             C₁-C₄-alkyl, a C₁-C₄-alkoxy, a C₁-C₄-halogenoalkoxy having 1             to 5 halogen atoms or a C₁-C₄-alkylthio; and         -   R³⁷ may be a hydrogen atom, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a             hydroxy-C₁-C₄-alkyl, a C₂-C₆-alkenyl, a C₃-C₆-cycloalkyl, a             C₁-C₄-alkylthio-C₁-C₄-alkyl, a             C₁-C₄-halogenoalkylthio-C₁-C₄-alkyl having 1 to 5 halogen             atoms, a C₁-C₄-alkoxy-C₁-C₄-alkyl, a             C₁-C₄-halogenoalkoxy-C₁-C₄-alkyl having 1 to 5 halogen atoms             or a phenyl optionally substituted by a halogen atom, a             C₁-C₄-alkyl, a C₁-C₄-alkoxyalkyl or a nitro group.     -   Het represents a heterocycle of the general formula (XV)

-   -    in which:         -   R³⁸ may be a hydrogen atom, a halogen atom, a cyano group, a             nitro group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1             to 5 halogen atoms, a C₃-C₆-cycloalkyl, a C₁-C₄-alkoxy, a             C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a             C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5             halogen atoms, an aminocarbonyl, or an             aminocarbonyl-C₁-C₄-alkyl;         -   R³⁹ may be a hydrogen atom, a halogen atom, a cyano group, a             C₁-C₄-alkyl, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio or a             C₁-C₄-halogenoalky having 1 to 5 halogen atoms;         -   R⁴⁰ may be a hydrogen atom, a phenyl, a benzyl, a             C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen             atoms, a hydroxy-C₁-C₄-alkyl, a C₂-C₆-alkenyl, a             C₃-C₆-cycloalkyl, a C₁-C₄-alkylthio-C₁-C₄-alkyl, a             C₁-C₄-halogenoalkylthio-C₁-C₄-alkyl having 1 to 5 halogen             atoms, a C₁-C₄-alkoxy-C₁-C₄-alkyl, a             C₁-C₄-halogenoalkoxy-C₁-C₄-alkyl having 1 to 5 halogen             atoms.     -   Het represents a heterocycle of the general formula (XVI)

-   -    in which R⁴¹ and R⁴² may be the same or different and may be a         hydrogen atom, a halogen atom, a C₁-C₄-alkyl or a         C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (XVII)

-   -    in which R⁴³ and R⁴⁴ may be the same or different and may be a         hydrogen atom, a halogen atom, a C₁-C₄-alkyl, a         C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a phenyl         optionally substituted by a halogen atom or a C₁-C₄-alkyl, or a         heterocyclyl optionally substituted by a halogen atom or a         C₁-C₄-alkyl.     -   Het represents a heterocycle of the general formula (XVIII)

-   -    in which R⁴⁵ and R⁴⁶ may be the same or different and may be a         hydrogen atom, a halogen atom, a C₁-C₄-alkyl or a         C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (XIX)

-   -    in which R⁴⁷ may be a halogen atom, a C₁-C₄-alkyl or a         C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (XX)

-   -    in which:         -   R⁴⁸ may be a halogen atom, a C₁-C₄-alkyl or a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms; and         -   R⁴⁹ may be a hydrogen atom, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, or a phenyl             optionally substituted by a halogen atom or a C₁-C₄-alkyl.     -   Het represents a heterocycle of the general formula (XXI)

-   -    in which R⁵⁰ may be a halogen atom, a C₁-C₄-alkyl or a         C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms.

According to the present invention, “Het” of the compound of general formula (I) may be a six membered ring non-fused heterocycle. Specific examples of compounds of the present invention where Het is a six membered heterocycle include:

-   -   Het represents a heterocycle of the general formula (XXII)

-   -    in which:         -   R⁵¹ may be a hydrogen atom, a halogen atom, a hydroxy group,             a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1             to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-akylthio, a             C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms or a             C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms;         -   R⁵², R⁵³ and R⁵⁴, which may be the same or different, may be             a hydrogen atom, a halogen atom, a cyano group, a             C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen             atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a             C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a             C₁-C₄-alkylsulphinyl or a C₁-C₄-alkylsulphonyl.     -   Het represents a heterocycle of the general formula (XXIII)

-   -    in which:         -   R⁵⁵ may be a hydrogen atom, a halogen atom, a hydroxy group,             a cyano group, an amino group, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a             C₁-C₄-alkoxy, a C₁-C₅-alkylthio, a C₂-C₅-alkenylthio a             C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a             C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a             phenyloxy optionally substituted by a halogen atom or a             C₁-C₄-alkyl, or a phenylthio optionally substituted by a             halogen atom or a C₁-C₄-alkyl;         -   R⁵⁶, R⁵⁷ and R⁵⁸, which may the same or different, may be a             hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl,             a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a             C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkoxy             having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl, a             C₁-C₄-alkylsulphonyl or a N-morpholine optionally             substituted by a halogen atom or a C₁-C₄-alkyl, or a thienyl             optionally substituted by a halogen atom or a C₁-C₄-alkyl.     -   Het represents a heterocycle of the general formula (XXIV)

-   -    in which R⁵⁹, R⁶⁰, R⁶¹ and R⁶², which may be the same or         different, may be a hydrogen atom, a halogen atom, a hydroxy         group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl         having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio,         a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a         C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a         C₁-C₄-alkylsulphinyl or a C₁-C₄-alkylsulphonyl.     -   Het represents a heterocycle of the general formula (XXV)

-   -    in which:         -   R⁶³ may be a hydrogen atom, a halogen atom, a C₁-C₄-alkyl or             a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms;         -   R⁶⁴ may be a hydrogen atom, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a             C₁-C₆-alkoxycarbonyl, a benzyl optionally substituted by 1             to 3 halogen atoms, a benzyloxycarbonyl optionally             substituted by 1 to 3 halogen atoms or a heterocyclyl.     -   Het represents a heterocycle of the general formula (XXVI)

-   -    in which:         -   R⁶⁵ may be a hydrogen atom, a halogen atom, a hydroxy group,             a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1             to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a             C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms or a             C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms;         -   R⁶⁶ may be a hydrogen atom, a C₁-C₄-alkyl, a             C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms or a benzyl.     -   Het represents a heterocycle of the general formula (XXVII)

-   -    in which:         -   X¹ may be a sulphur atom, —SO—, —SO₂— or —CH₂—;         -   R⁶⁷ may be a C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1             to 5 halogen atoms; and         -   R⁶⁸ and R⁶⁹ may be the same or different and may be a             hydrogen atom or a C₁-C₄-alkyl.     -   Het represents a heterocycle of the general formula (XXVIII)

-   -    in which:         -   R⁷⁰ may be a C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1             to 5 halogen atoms;     -   Het represents a heterocycle of the general formula (XXIX)

-   -    in which:         -   R⁷¹ may be a C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1             to 5 halogen atoms.     -   Het represents a heterocycle of the general formula (XXX)

-   -    in which R⁷² may be a hydrogen atom, a halogen atom, a         C₁-C₄-alkyl or a C₁-C₄-halogenoalkyl having 1 to 5 halogen         atoms.

The present invention also relates to a process for the preparation of the compound of general formula (I). Thus, according to a further aspect of the present invention there is provided a process for the preparation of compound of general formula (I) as defined above, which comprises reacting a carboxylic acid derivative of the general formula (A)

in which:

-   -   Het is as defined above;     -   G may be a halogen atom, a hydroxy group or a C₁-C₆-alkoxy;         with a 2-pyridine derivative of general formula (B)

in which Y, R¹ and n are as defined above;

in the presence of a catalyst if G is a hydroxy or a C₁-C₆-alkoxy group, or in the presence of an acid binder if G is a halogen atom.

According to the present invention, the process for the preparation of compound of general formula (I) is carried out in the presence of a catalyst if G is a hydroxy or a C₁-C₆-alkoxy group. Suitable catalyst includes the coupling reagents dicyclohexylcarbodiimide, N,N′-carbonyldimidazole, bromotripyrrolidinophosphonium hexafluorophosphate and trimethylaluminium.

According to the present invention, the process for the preparation of compound of general formula (I) is carried out in the presence of an acid binder if G is a halogen atom. Suitable acid binder includes carbonates, aqueous alkali or tertiary amines.

The present invention also relates to another process for the preparation of the compound of general formula (I). Thus, according to a further aspect of the present invention there is provided a second process for the preparation of compound of general formula (I) as defined above, which comprises reacting a carboxylic acid anhydride derivative of general formula (C)

in which:

-   -   Het is as defined above;     -   W maybe defined as Het or a C₁-C₆-alkyl;         with a 2-pyridine derivative of the formula (D)

in which R¹ and n are each as defined above;

in the presence of a reducing agent.

According to the present invention, the second process for the preparation of compound of general formula (I) is carried out in the presence of a reducing agent. Suitable reducing agent includes H₂ and NaBH₄.

The compound according to the present invention can be prepared according to the general processes of preparation described above. It will nevertheless be understood that the skilled worker will be able to adapt this method according to the specifics of each of the compounds, which it is desired to synthesise. For example, the above mentioned processes may be carried out in the presence of a diluent if appropriate. If appropriate, the second process for the preparation of compound of general formula (I) may also be carried out in the presence of a catalyst such as NiCl₂—H₂O or CoCl₃—H₂O.

Certain of the intermediate compounds used for the preparation of compound of general formula (I) are novel. Therefore, the present invention also relates to novel intermediate compound useful for the preparation of compound of general formula (I). Thus, according to the present invention, there is provided a novel compound of general formula (E):

in which:

-   -   Z may be the same or different and may be a halogen atom, a         nitro group, a cyano group, a hydroxy, a carboxyl group, a         C₁-C₈-alkyl, a C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms,         a C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, a         C₁-C₈-alkylthio, a C₁-C₆-halogenoalkylthio having 1 to 5 halogen         atoms, a C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1         to 5 halogen atoms, a C₃-C₈-alkinyloxy, a         C₃-C₈-halogenoalkinyloxy having 1 to 5 halogen atoms, a         C₃-C₈-cycloalkyl, a C₁-C₈-alkoxycarbonyl, a         C₁-C₈-alkylsulphinyl, a C₁-C₈-alkylsulphonyl, a         C₁-C₈-halogenoalkylsulphinyl having 1 to 5 halogen atoms, a         C₁-C₈-halogenoalkyl-sulphonyl having 1 to 5 halogen atoms or a         C₁-C₆-alkoximino-C₁-C₆-alkyl;     -   Z¹ may be a halogen atom or a C₁-C₈-alkyl;     -   R¹ and n are as defined above.

The present invention also relates to a fungicidal composition comprising an effective amount of an active material of general formula (I). Thus, according to the present invention, there is provided a fungicidal composition comprising, as an active ingredient, an effective amount of a compound of general formula (I) as defined above and an agriculturally acceptable carrier or filler.

In the present specification, the term “support” denotes a natural or synthetic, organic or inorganic material with which the active material is combined to make it easier to apply, notably to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support may be a solid or a liquid. Examples of suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol, organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports may also be used.

The composition may also comprise additional components. In particular, the composition may further comprise a surfactant. The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention may be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the above compounds containing sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential when the active material and/or the inert support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content may be between 5% and 40% by weight.

Optionally, additional components may also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active materials can be combined with any solid or liquid additive, which complies with the usual formulation techniques.

In general, the composition according to the invention may contain from 0.05 to 99% (by weight) of active material, preferably 10 to 70% by weight.

Compositions according to the present invention can be used in various forms such as aerosol dispenser, bait (ready for use), bait concentrate, block bait, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, grain bait, granular bait, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, plate bait, powder for dry seed treatment, scrap bait, seed coated with a pesticide, smoke candle, smoke cartridge, smoke generator, smoke pellet, smoke rodlet, smoke tablet, smoke tin, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), tracking powder, ultra low volume (ulv) liquid, ultra low volume (ulv) suspension, vapour releasing product, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder.

These compositions include not only compositions which are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concentrated commercial compositions which must be diluted before they are applied to the crop.

The compounds of the invention can also be mixed with one or more insecticides, fungicides, bactericides, attractant acaricides or pheromones or other compounds with biological activity. The mixtures thus obtained have a broadened spectrum of activity. The mixtures with other fungicides are particularly advantageous.

The fungicidal compositions of the present invention can be used to curatively or preventively control the phytopathogenic fungi of crops. Thus, according to a further aspect of the present invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of crops characterised in that a fungicidal composition as hereinbefore defined is applied to the seed, the plant and/or to the fruit of the plant or to the soil in which the plant is growing or in which it is desired to grow.

The composition as used against phytopathogenic fungi of crops comprises an effective and non-phytotoxic amount of an active material of general formula (I).

The expression “effective and non-phytotoxic amount” means an amount of composition according to the invention which is sufficient to control or destroy the fungi present or liable to appear on the crops, and which does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus to be combated, the type of crop, the climatic conditions and the compounds included in the fungicidal composition according to the invention.

This amount can be determined by systematic field trials, which are within the capabilities of a person skilled in the art.

The method of treatment according to the present invention is useful to treat propagation material such as tubers and rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots. The method of treatment according to the present invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruits of the concerned plant.

Among the plants targeted by the method according to the invention, mention may be made of cotton; flax; vine; fruit crops such as Rosaceae sp. (for instance pip fruits such as apples and pears, but also stone fruits such as apricots, almonds and peaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana trees and plantins), Rubiaceae sp., Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges and grapefruits); leguminous crops such as Solanaceae sp. (for instance tomatoes), Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp. (for instance strawberries); big crops such as Graminae sp. (for instance maize, cereals such as wheat, rice, barley and triticale), Asteraceae sp. (for instance sunflower), Cruciferae sp. (for instance colza), Papilionaceae sp. (for instance soja), Solanaceae sp. (for instance potatoes), Chenopodiaceae sp. (for instance beetroots); horticultural and forest crops; as well as genetically modified homologues of these crops.

Among the plants and the possible diseases of these plants targeted by the method according to the present invention, mention may be made of:

-   -   wheat, as regards controlling the following seed diseases:         fusaria (Microdochium nivale and Fusarium roseum), stinking smut         (Tilletia caries, Tilletia controversa or Tilletia indica),         septoria disease (Septoria nodorum) and loose smut;     -   wheat, as regards controlling the following diseases of the         aerial parts of the plant: cereal eyespot (Tapesia yallundae,         Tapesia acuiformis), take-all (Gaeumannomyces graminis), foot         blight (F. culmorum, F. graminearum), black speck (Rhizoctonia         cerealis), powdery mildew (Erysiphe graminis forma specie         tritici), rusts (Puccinia striiformis and Puccinia recondita)         and septoria diseases (Septoria tritici and Septoria nodorum);     -   wheat and barley, as regards controlling bacterial and viral         diseases, for example barley yellow mosaic;     -   barley, as regards controlling the following seed diseases: net         blotch (Pyrenophora graminea, Pyrenophora teres and Cochliobolus         sativus), loose smut (Ustilago nuda) and fusaria (Microdochium         nivale and Fusarium roseum);     -   barley, as regards controlling the following diseases of the         aerial parts of the plant: cereal eyespot (Tapesia yallundae),         net blotch (Pyrenophora teres and Cocliliobolus sativus),         powdery mildew (Erysiphe graminis forma specie hordei), dwarf         leaf rust (Puccinia hordei) and leaf blotch (Rhynchosporium         secalis);     -   potato, as regards controlling tuber diseases (in particular         Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani,         Fusarium solani), mildew (Phytopthora infestans) and certain         viruses (virus Y);     -   potato, as regards controlling the following foliage diseases:         early blight (Alternaria solani), mildew (Phytophthora         infestans);     -   cotton, as regards controlling the following diseases of young         plants grown from seeds: damping-off and collar rot (Rhizoctonia         solani, Fusarium oxysporum) and black root rot (Thielaviopsis         basicola);     -   protein yielding crops, for example peas, as regards controlling         the following seed diseases: anthracnose (Ascochyta pisi,         Mycosphaerella pinodes), fusaria (Fusarium oxysporum), grey         mould (Botrytis cinerea) and mildew (Peronospora pisi);     -   oil-bearing crops for example rape, as regards controlling the         following seed diseases: Phoma lingam, Alternaria brassicae and         Sclerotinia sclerotiorum;     -   corn, as regards controlling seed diseases: (Rhizopus sp.,         Penicillium sp., Trichoderma sp., Aspergillus sp., and         Gibberella fujikuroi);     -   flax, as regards controlling the seed disease: Alternaria         linicola;     -   forest trees, as regards controlling damping-off (Fusarium         oxysporum, Rhizoctonia solani);     -   rice, as regards controlling the following diseases of the         aerial parts: blast disease (Magnaporthe grisea), bordered         sheath spot (Rhizoctonia solani);     -   leguminous crops, as regards controlling the following diseases         of seeds or of young plants grown from seeds: damping-off and         collar rot (Fusarium oxysporum, Fusarium roseum, Rhizoctonia         solani, Pythium sp.);     -   leguminous crops, as regards controlling the following diseases         of the aerial parts: grey mould (Botrytis sp.), powdery mildews         (in particular Erysiphe cichoracearum, Sphaerotheca fuliginea         and Leveillula taurica), fusaria (Fusarium oxysporum, Fusarium         roseum), leaf spot (Cladosporium sp.), alternaria leaf spot         (Alternaria sp.), anthracnose (Colletotrichum sp.), septoria         leaf spot (Septoria sp.), black speck (Rhizoctonia solani),         mildews (for example Bremia lactucae, Peronospora sp.,         Pseudoperonospora sp., Phytophthora sp.);     -   fruit trees, as regards diseases of the aerial parts: monilia         disease (Monilia fructigenae, M. laxa), scab (Venturia         inaequalis), powdery mildew (Podosphaera leucotricha);     -   vine, as regards diseases of the foliage: in particular grey         mould (Botrytis cinerea), powdery mildew (Uncinula necator),         black rot (Guignardia biwelli) and mildew (Plasmopara viticola);     -   beetroot, as regards the following diseases of the aerial parts:         cercospora blight (Cercospora beticola), powdery mildew         (Erysiphe beticola), leaf spot (Ramularia beticola).

The fungicide composition according to the present invention may also be used against fungal diseases liable to grow on or inside timber. The term “timber” means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds of the present invention, or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.

The dose of active material usually applied in the treatment according to the present invention is generally and advantageously between 10 and 800 g/ha, preferably between 50 and 300 g/ha for applications in foliar treatment. The dose of active material applied is generally and advantageously between 2 and 200 g per 100 kg of seed, preferably between 3 and 150 g per 100 kg of seed in the case of seed treatments. It is clearly understood that the doses indicated above are given as illustrative examples of the invention. A person skilled in the art will know how to tailor the application doses according to the nature of the crop to be treated.

The fungicidal composition according to the present invention may also be used in the treatment of genetically modified organisms with the compounds according to the invention or the agrochemical compositions according to the invention. Genetically modified plants are plants into whose genome a heterologous gene encoding a protein of interest has been stably integrated. The expression “heterologous gene encoding a protein of interest” essentially means genes which give the transformed plant new agronomic properties, or genes for improving the agronomic quality of the transformed plant.

The compositions according to the present invention may also be used to curatively or preventively treat human and animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.

The aspects of the present invention will now be illustrated with reference to the following tables of compounds and examples. The following Tables A to V illustrate in a non-limiting manner examples of fungicidal compounds according to the present invention. In the following Examples, M+1 (or M−1) means the molecular ion peak, plus or minus 1 a.m.u. (atomic mass units) respectively, as observed in mass spectroscopy and M (ApcI+) means the molecular ion peak as it was found via positive atmospheric pressure chemical ionisation in mass spectroscopy.

TABLE A

Compound R¹ R² R³ R⁴ Y¹ Y² Y³ Y⁴ M + 1 A-1 H H H H Cl H CF₃ H 319 at 1 ³⁵Cl A-2 H NO₂ H H Cl H CF₃ H 364 at 1 ³⁵Cl A-3 H H H Me Cl H CF₃ H 333 at 1 ³⁵Cl A-4 H H H Br Cl H CF₃ H 397 at 1 ³⁵Cl and 1 ⁷⁹Br

TABLE B

Compound R¹ R⁵ R⁶ R⁷ Y¹ Y² Y³ Y⁴ M (ApcI+) M + 1 B-1 H Me H H Cl H CF₃ H 333 at 1 ³⁵Cl B-2 H CF₃ 4-chlorophenyl H Cl H CF₃ H 497 at 2 ³⁵Cl B-3 H H H H Cl H CF₃ H 319 at 1 ³⁵Cl B-4 H Me t-Bu H Cl H CF₃ H 389 at 1 ³⁵Cl B-5 H Me Ph H Cl H CF₃ H 409 at 1 ³⁵Cl B-6 H Me 4-chlorophenyl H Cl H CF₃ H 443 at 2 ³⁵Cl B-7 H Me Me H Cl H CF₃ H 347 at 1 ³⁵Cl B-8 H CF₃ Me H Cl H CF₃ H 401 at 1 ³⁵Cl B-9 H CF₃ 3-chlorophenyl H Cl H CF₃ H 496 at 2 ³⁵Cl B-10 H CF₃ Ph H Cl H CF₃ H 463 at 1 ³⁵Cl B-11 H H H Me Cl H CF₃ H 333 at 1 ³⁵Cl B-12 H CF₃ H H Cl H CF₃ H 387 at 1 ³⁵Cl B-13 H Me H H Cl H Cl H B-14 H I H H Cl H CF₃ H 445 at 1 ³⁵Cl B-15 Cyclopropyl I H H Cl H CF₃ H 485 at 1 ³⁵Cl B-16 H Me Me H Cl H Cl Me 327 at 2 ³⁵Cl B-17 H Me Me H F H F F 299 B-18 H I H H F H F F 397 B-19 H Me H H F H F F 285 B-20 H Me Me H F Me F F 313 B-21 H Me H H F Me F F 299 B-22 H I H H F Me F F 411

TABLE C

Compound R¹ R¹⁰ R¹¹ R¹² Y¹ Y² Y³ Y⁴ M (ApcI+) M + 1 C-1 H H H H Cl H CF₃ H 335 at 1 ³⁵Cl C-2 H H H Cl Cl H CF₃ H 369 at 2 ³⁵Cl C-3 H H H Me Cl H CF₃ H 349 at 1 ³⁵Cl C-4 H H SO₂iPr Cl Cl H CF₃ H 475 at 2 ³⁵Cl C-5 H H H Br Cl H CF₃ H 412 at 1 ³⁵Cl and 1 ⁷⁹Br C-6 H 2-Pyridyl H H Cl H CF₃ H 412 at 1 ³⁵Cl C-7 H Ph H H Cl H CF₃ H 411 at 1 ³⁵Cl C-8 H H SO₂Me Cl Cl H CF₃ H 446 at 1 ³⁵Cl C-9 H SMe SO₂iPr Cl Cl H CF₃ H 521 at 2 ³⁵Cl C-10 H SMe SO₂iPr I Cl H CF₃ H 612 at 1 ³⁵Cl C-11 H Cl Cl Cl Cl H CF₃ H 436 at 4 ³⁵Cl C-12 H H H I Cl H CF₃ H 461 at 1 ³⁵Cl C-13 H H H I Cl H Cl H C-14 H H H Me F H Cl H 333 at 1 ³⁵Cl C-15 H H H I F H Cl H 411 at 1 ³⁵Cl C-16 H H H I Br H Cl H 471 at 1 ³⁵Cl and 1 ⁷⁹Br C-17 H H H I H H Cl H 393 at 1 ³⁵Cl C-18 H H H I Cl H H Cl 427 at 2 ³⁵Cl C-19 H H H I H H Me H 373 C-20 Cyclopropyl H H I Cl H CF₃ H C-21 H H H I Cl H Cl Me 441 at 2 ³⁵Cl C-22 H H H I Cl H Cl F 445 at 2 ³⁵Cl C-23 H H H I F H Cl F C-24 H H H I H H CF₃ Cl 461 at 1 ³⁵Cl C-25 H H H Me H H CF₃ Cl C-26 H H H Me F H F F 301 C-27 H H H Br F H F F 365 at 1 ⁷⁹Br C-28 H H H I F H F F 413 C-29 H H H Me F Me F F 315 C-30 H H H Br F Me F F 379 at 1 ⁷⁹Br C-31 H H H I F Me F F 427

TABLE D

Com- pound R¹ R¹³ R¹⁴ R¹⁵ Y¹ Y² Y³ Y⁴ M + 1 D-1 H Cl OMe H Cl H CF₃ H 399 at 2 ³⁵Cl D-2 H H H H Cl H CF₃ H 335 at 1 ³⁵Cl D-3 H H H Me Cl H CF₃ H 349 at 1 ³⁵Cl D-4 H H H I Cl H CF₃ H 461 at 1 ³⁵Cl D-5 H H Me H Cl H CF₃ H 349 at 1 ³⁵Cl D-6 H H H I F H F F 413 at 1 ³⁵Cl D-7 H H H I F Me F F 427 at 1 ³⁵Cl

TABLE E

Compound R¹ R¹⁶ R¹⁷ R¹⁸ R¹⁹ Y¹ Y² Y³ Y⁴ M + 1 M − 1 E-1 H H Me Me Me Cl H CF₃ H 358 at 1 ³⁵Cl E-2 H CF₃ Me Me H Cl H CF₃ H 400 at 1 ³⁵Cl E-3 H CF₃ H Me H Cl H F F 352 E-4 H CF₃ H Me H Cl Me F F 366

TABLE F

Compound R¹ R²⁰ R²¹ R²² R²³ Y¹ Y² Y³ Y⁴ M (APcI+) M + 1 F-1 H Me H H H Cl H CF₃ H 332 at 1 ³⁵Cl F-2 H H Me Ac Me Cl H CF₃ H 387 at 1 ³⁵Cl F-3 H Me H H I Cl H CF₃ H 458 at 1 ³⁵Cl

TABLE G

Compound R¹ R²⁶ R²⁷ Y¹ Y² Y³ Y⁴ M + 1 G-1 H H Ph Cl H CF₃ H 396 at 1 ³⁵Cl G-2 H Me CF₃ Cl H CF₃ H 402 at 1 ³⁵Cl

TABLE H

Com- pound R¹ R²⁸ R²⁹ Y¹ Y² Y³ Y⁴ M + 1 H-1 H Me CF₃ Cl H CF₃ H 418 at 1 ³⁵Cl H-2 H Me CHF₂ Cl H CF₃ H 400 at 1 ³⁵Cl H-3 H Ph Me Cl H CF₃ H 426 at 1 ³⁵Cl H-4 H Me CF₃ Cl H Cl H H-5 H Me CF₃ Cl H H Cl 384 at 2 ³⁵Cl H-6 H Me CF₃ Cl H Methoxy- H 407 at 1 ³⁵Cl iminoethyl H-7 H Me CF₃ Cl H Ethoxy- H 421 at 1 ³⁵Cl imino- methyl H-8 H Me CF₃ Cl H Isopropox- H 435 at 1 ³⁵Cl iminoethyl H-9 H Me CF₃ Cl H Cl Cl 418 at 3 ³⁵Cl H-10 H Me CF₃ F H Cl H 368 at 1 ³⁵Cl H-11 Cyclo- Me CF₃ Cl H CF₃ H 458 at 1 ³⁵Cl propyl H-12 H Me CF₃ F Me F F 384 H-13 H Me CF₃ Cl H Cl Me 398 at 2 ³⁵Cl H-14 H Me CF₃ F H F F 370 H-15 Cyclo- Me CHF₂ Cl H CF₃ H 440 at 1 ³⁵Cl propyl H-16 H Me CHF₂ F Me F F 366 H-17 H Me CHF₂ Cl H Br H 409 at 1 ³⁵Cl and 1 ⁷⁹Br H-18 H Me CHF₂ Br H CF₃ H 444 at 1 ⁷⁹Br H-19 H Me CHF₂ Cl H Cl Me 380 at 2 ³⁵Cl H-20 H Me CHF₂ Cl H Cl F 384 at 2 ³⁵Cl H-21 H Me CHF₂ F H F F 352 H-22 H Me CHF₂ F H Cl F 368 at 1 ³⁵Cl H-23 H Me CHF₂ H H CF₃ Cl 400 at 1 ³⁵Cl

TABLE I

Compound R¹ R³² R³³ R³⁴ Y¹ Y² Y³ Y⁴ M (APcI+) M + 1 I-1 H H Me t-Bu Cl H CF₃ H 389 at 1 ³⁵Cl I-2 H H Me Me Cl H CF₃ H 347 at 1 ³⁵Cl I-3 H Br NO₂ Me Cl H CF₃ H 455 at 1 ³⁵Cl and 1 ⁷⁹Br I-4 H I H Me Cl H CF₃ H 459 at 1³⁵Cl

TABLE J

Compound R¹ R³⁵ R³⁶ R³⁷ Y¹ Y² Y³ Y⁴ M + 1 J-1 H Me F Me Cl H CF₃ H 365 at 1 ³⁵Cl J-2 H Me H Me Cl H CF₃ H 347 at 1 ³⁵Cl J-3 H CHF₂ H Me Cl H CF₃ H 383 at 1 ³⁵Cl J-4 H H CF₃ Ph Cl H CF₃ H 463 at 1 ³⁵Cl J-5 H H CF₃ 4-chlorophenyl Cl H CF₃ H 497 at 2 ³⁵Cl J-6 H H Cl Me Cl H CF₃ H 367 at 2 ³⁵Cl J-7 H H Me 4-fluorophenyl Cl H CF₃ H 427 at 1 ³⁵Cl J-8 H H Me 4-methoxyphenyl Cl H CF₃ H 439 at 1 ³⁵Cl J-9 H H Me Ph Cl H CF₃ H 409 at 1 ³⁵Cl J-10 H H Me 2-methylphenyl Cl H CF₃ H 423 at 1 ³⁵Cl J-11 H H n-Pr Ph Cl H CF₃ H 437 at 1 ³⁵Cl J-12 H H n-Pr 4-chlorophenyl Cl H CF₃ H 471 at 2 ³⁵Cl J-13 H H CF₃ 4-nitrophenyl Cl H CF₃ H 508 at 1 ³⁵Cl J-14 H Me Me Me Cl H CF₃ H 361 at 1 ³⁵Cl J-15 H Cl H Me Cl H CF₃ H 367 at 2 ³⁵Cl J-16 H I H Me Cl H CF₃ H 459 at 1 ³⁵Cl J-17 H Me Me Me Cl H Cl H J-18 H Me F Me Cl H Cl H 330 at 2 ³⁵Cl J-19 H Me H Me Cl H Cl H J-20 H CF₃ H Me Cl H Cl Cl 401 at 3 ³⁵Cl J-21 H CF₃ H Me F H Cl H 351 at 1 ³⁵Cl J-22 H CF₃ H Me Cl H H Cl 365 at 2 ³⁵Cl J-23 Cyclopropyl CF₃ H Me Cl H CF₃ H 441 at 1 ³⁵Cl J-24 H CF₃ H Me H H CF₃ Cl 401 at 1 ³⁵Cl J-25 H CF₃ H Me Cl H Cl Me 381 at 2 ³⁵Cl J-26 H CF₃ H Me Cl H Cl F 385 at 2 ³⁵Cl J-27 H CF₃ H Me F H F F 353 J-28 H CF₃ H Me F Me F F 367 J-29 H CHF₂ H Me Cl H Cl H J-30 H CHF₂ H Me H H Me H 295 J-31 H CHF₂ H Me H H Methoximinoethyl H 386 at 1 ³⁵Cl J-32 H CHF₂ H Me Me H Br H J-33 H CHF₂ H Me F H Cl H 333 at 1 ³⁵Cl J-34 H CHF₂ H Me Cl H Cl Cl 383 at 3 ³⁵Cl J-35 H CHF₂ H Me Cl H Methoximinoethyl H 372 at 1 ³⁵Cl J-36 H CHF₂ H Me H H Cl H J-37 H CHF₂ H Me Cl H Ethoximinoethyl H 386 at 1 ³⁵Cl J-38 H CHF₂ H Me Cl H Isopropoxyiminoethyl H J-39 H CHF₂ H Me Br H Cl H 393 at 1 ³⁵Cl and 1 ⁷⁹Br J-40 H CHF₂ H Me F Me F F 349 J-41 Cyclopropyl CHF₂ H Me Cl H CF₃ 423 at 1 ³⁵Cl J-42 H CHF₂ H Me H H CF₃ 383 at 1 ³⁵Cl J-43 H CHF₂ H Me Cl H Br J-44 H CHF₂ H Me F H Cl 351 at 1 ³⁵Cl J-45 H CHF₂ H Me Br H CF₃ 417 at 1 ⁷⁹Br J-46 H Me F Me Cl H Cl J-47 H Me F Me H H Me 277 J-48 H Me F Me Cl H Methoximinoethyl H J-49 H Me F Me F H Cl H 315 at 1 ³⁵Cl J-50 H Me F Me Cl H Cl Cl 365 at 3 ³⁵Cl J-51 H Me F Me Cl H Methoximinoethyl H 354 at 1 ³⁵Cl J-52 Cyclopropyl Me F Me Cl H CF₃ H 405 at 1 ³⁵Cl J-53 H Me F Me F H F H 317 J-54 H CF₃ H Me Cl H CF₃ H J-55 H Fluorethyl H Me Cl H CF₃ H J-56 H Formyl H Me Cl H CF₃ H J-57 H Cl H Me Cl H CF₃ H J-58 H I H Me Cl H CF₃ H J-59 H Me H Me Cl H CF₃ H J-60 H CHCl₂ H Me Cl H CF₃ H J-61 H H Fluorethyl Me Cl H CF₃ H

TABLE K

Com- pound R¹ R³⁸ R³⁹ R⁴⁰ Y¹ Y² Y³ Y⁴ M + 1 K-1 H Me H t-Bu Cl H CF₃ H 389 at 1 ³⁵Cl K-2 H t-Bu H Me Cl H CF₃ H 334 at 1 ³⁵Cl K-3 H t-Bu H Benzyl Cl H CF₃ H 465 at 1 ³⁵Cl K-4 H Me H Me Cl H CF₃ H 347 at 1 ³⁵Cl K-5 H H H Ph Cl H CF₃ H 395 at 1 ³⁵Cl K-6 H Me Br Et Cl H CF₃ H 439 at 1 ³⁵Cl and 1 ⁷⁹Br

TABLE L

Compound R¹ R⁴¹ R⁴² Y¹ Y² Y³ Y⁴ M + 1 L-1 H Me H Cl H CF₃ H 394 at 1 ³⁵Cl

TABLE M

Compound R¹ R⁴³ R⁴⁴ Y¹ Y² Y³ Y⁴ M − 1 M + 1 M-1 H Me 4-methyl-[1,2,3]thiadiazol-5-yl Cl H CF₃ H 432 at 1 ³⁵Cl M-2 H Me Me Cl H CF₃ H 348 at 1 ³⁵Cl M-3 H Ph Me Cl H CF₃ H 408 at 1 ³⁵Cl M-4 H 2-chlorophenyl Me Cl H CF₃ H 444 at 2 ³⁵Cl M-5 H 2,6-dichlorophenyl Me Cl H CF₃ H 478 at 3 ³⁵Cl M-6 H 2-chloro-6-fluorophenyl Me Cl H CF₃ H 462 at 2 ³⁵Cl M-7 H 4-chlorophenyl Me Cl H CF₃ H 444 at 1 ³⁵Cl

TABLE N

Compound R¹ R⁴⁵ R⁴⁶ Y¹ Y² Y³ Y⁴ M + 1 N-1 H H H Cl H CF₃ H 320 at 1 ³⁵Cl

TABLE O

Compound R¹ R⁴⁸ R⁴⁹ Y¹ Y² Y³ Y⁴ M + 1 O-1 H Me Ph Cl H CF₃ H 410 at 1 ³⁵Cl

TABLE P

Compound R¹ R⁵⁰ Y¹ Y² Y³ Y⁴ M + 1 P-1 H Me Cl H CF₃ H 351 at 1 ³⁵Cl

TABLE Q

Compound R¹ R⁵¹ R⁵² R⁵³ R⁵⁴ Y¹ Y² Y³ Y⁴ M (APcI+) M + 1 Q-1 H Cl H CF₃ H Cl H CF₃ H 432 at 2 ³⁵Cl Q-2 H Cl H H Cl Cl H CF₃ H 397 at 3 ³⁵Cl Q-3 H Me H H H Cl H CF₃ H 344 at 1 ³⁵Cl

TABLE R

Com- pound R¹ R⁵⁵ R⁵⁶ R⁵⁷ R⁵⁸ Y¹ Y² Y³ Y⁴ M (ApcI+) M + 1 R-1 H Cl H H H Cl H CF₃ H 364 at 2 ³⁵Cl R-2 H Cl H H H Cl H Cl H R-3 H SEt H H H Cl H CF₃ H 390 at 1 ³⁵Cl R-4 H H Cl H H Cl H CF₃ H 364 at 2 ³⁵Cl R-5 H H H H H Cl H CF₃ H 330 at 1 ³⁵Cl R-6 H SPh H H H Cl H CF₃ H 438 at 1 ³⁵Cl R-7 H 4-chlorophenoxy H H H Cl H CF₃ H 456 at 2 ³⁵Cl R-8 H H H 2-Thienyl H Cl H CF₃ H 412 at 1 ³⁵Cl R-9 H H N-Morpholino H H Cl H CF₃ H 415 at 1 ³⁵Cl R-10 H Me H H H Cl H CF₃ H 344 at 1 ³⁵Cl R-11 H 3-propenyl- H H H Cl H CF₃ H 402 at 1 ³⁵Cl sulfinyl R-12 H SnPr H H H Cl H CF₃ H 404 at 1 ³⁵Cl R-13 H n-pentylsulfinyl H H H Cl H CF₃ H 432 at 1 ³⁵Cl R-14 H Cl Cl F H Cl H CF₃ H 415 at 3 ³⁵Cl R-15 H Me CF₃ H H Cl H CF₃ H 412 at 1 ³⁵Cl R-16 H CN H H H Cl H CF₃ H 355 at 1 ³⁵Cl R-17 H Cl Me H H Cl H CF₃ H 378 at 2 ³⁵Cl R-18 H CF₃ H H H Cl H CF₃ H 398 at 1 ³⁵Cl R-19 H F H H H Cl H CF₃ H 348 at 1 ³⁵Cl R-20 H H H H CF₃ Cl H CF₃ H 398 at 1 ³⁵Cl R-21 H Cl Cl H H Cl H CF₃ H 397 at 3 ³⁵Cl 398 at 3 ³⁵Cl R-22 H Cl H Cl H Cl H CF₃ H 397 at 3 ³⁵Cl 398 at 3 ³⁵Cl R-23 H Cl H H H Cl H 1-methoximinoethyl H 367 at 2 ³⁵Cl R-24 H Cl H H H F H Cl H 314 at 2 ³⁵Cl R-25 H NH₂ H H H Cl H CF₃ H 345 at 1 ³⁵Cl R-26 H Br H H H Cl H CF₃ H 408 at 1 ³⁵Cl and 1 ⁷⁹Br R-27 H H H H H Cl H CF₃ H 456 at 1 ³⁵Cl R-28 H SH H H H Cl H CF₃ H 362 at 1 ³⁵Cl R-29 H Cl H H H Cl H Cl H 364 at 4 ³⁵Cl R-30 H Cl H H H Cl H Methoximinoethyl H 353 at 2 ³⁵Cl R-31 H Cl H H H Cl H Ethoximinoethyl H 367 at 2 ³⁵Cl R-32 H Cl H H H H H Cl H 296 at 2 ³⁵Cl R-33 Cyclopropyl Cl Me H H Cl H CF₃ H 418 at 2 ³⁵Cl R-37 H Cl Cl H CF₃ Cl H CF₃ H 466 at 3 ³⁵Cl R-35 H Cl Me H H F Me F F 344 at 1 ³⁵Cl R-36 H Cl Me H H F H F F 330 at 1 ³⁵Cl

TABLE S

Compound R¹ R⁵⁹ R⁶⁰ R⁶¹ R⁶² Y¹ Y² Y³ Y⁴ M + 1 S-1 H H Cl Cl H Cl H CF₃ H 398 at 3 ³⁵Cl S-2 H H Me Cl H Cl H CF₃ H 378 at 2 ³⁵Cl S-3 H H OMe Cl H Cl H CF₃ H 330 at 2 ³⁵Cl S-4 H H H H H Cl H CF₃ H 330 at 1 ³⁵Cl S-5 H H H Cl H Cl H CF₃ H 364 at 2 ³⁵Cl S-6 H NH₂ H H H Cl H CF₃ H 345 at 1 ³⁵Cl S-7 H I H H H Cl H CF₃ H 456 at 1 ³⁵Cl S-8 H Br H H H Cl H CF₃ H 408 at 1 ³⁵Cl and 1 ⁷⁹Br

TABLE T

Compound R¹ R⁶³ R⁶⁴ Y¹ Y² Y³ Y⁴ M + 1 T-1 H H Benzyloxycarbonyl Cl H CF₃ H 470 at 1 ³⁵Cl T-2 H H 4-trifluormethyl-pyrimidin-2-yl Cl H CF₃ H 482 at 1 ³⁵Cl

TABLE U

Compound R¹ R⁶⁵ R⁶⁶ Y¹ Y² Y³ Y⁴ M + 1 U-1 H H Benzyl Cl H CF₃ H 428 at 1 ³⁵Cl

TABLE V

Compound R¹ R⁶⁷ R⁶⁸ R⁶⁹ X¹ Y¹ Y² Y³ Y⁴ M + 1 V-1 H Me H H S Cl H CF₃ H 367 at 1 ³⁵Cl V-2 H CF₃ H H S Cl H CF₃ H 421 at 1 ³⁵Cl V-3 H CF₃ Me H S Cl H CF₃ H 435 at 1 ³⁵Cl V-4 H CF₃ H Me S Cl H CF₃ H 435 at 1 ³⁵Cl V-5 H CHF₂ H H S Cl H CF₃ H V-6 H Me H H S Cl H Cl H V-7 H Me H H S Cl H Cl Cl 521 at 3 ³⁵Cl V-8 H Me H H S Cl H Methoximinomethyl H 356 at 1 ³⁵Cl V-9 H Me H H S F H Cl H 335 at 1 ³⁵Cl V-10 H Me H H S Cl H H Cl 333 at 2 ³⁵Cl V-11 H CF₃ H H S H H Me H 333 V-12 Cyclopropyl Me H H S Cl H CF₃ H 407 at 1 ³⁵Cl V-13 Cyclopropyl CF₃ H H S Cl H CF₃ H 461 at 1 ³⁵Cl V-14 H CF₃ H H S F H F F 373 V-15 H Me H H S F H F F 319 V-16 H CF₃ H H S F Me F F 387 V-17 H Me H H S F Me F F 333

EXAMPLES OF PROCESS FOR PREPARATION OF THE COMPOUND OF GENERAL FORMULA (I) Example A Preparation of N-[2-(3-Chloro-5-trifluoromethyl-pyridin-2-yl) ethyl]-2-trifluoromethyl-nicotinamide

A solution of 204 mg (1 mmol) of 2-trifluormethyl nicotinic acid, 200 mg (0.9 mmol) of 2-(3-chloro-5-trifluormethyl-pyridin-2-yl)-ethylamine and 620 mg (1.3 mmol) of bromotripyrrolidinophosphonium hexafluorophosphate and 230 mg (1.8 mmol) N,N-Diisopropylethylamine in 8 ml methylene chloride is stirred for 20 h at room temperature.

The mixture is diluted with 10 ml water, separated and the methylene chloride phase is washed with sat. NH4Cl solution and water. The organic phase is dried over sodium sulfate. After evaporation of the solvent the residue is purified by column chromatography over silica-gel (eluant:hexane/ethylacetate=10:1 to 1:1). Yield: 370 mg (98%).

Example B Preparation of 2-Chloro-N-[2-(3-chloro-5-trifluoromethyl-pyrdin-2-yl)-ethyl]-6-methyl-nicotinamide

A solution of 161 mg (0.7 mmol) 2-chloro-6-methylnictotinyl chloride, 160 mg (0.7 mmol) 2-(3-chloro-5-trifluormethyl-pyridin-2-yl)-ethylamine hydrochloride and 236 mg (1.7 mmol) sodium carbonate in 8 ml acetonitrile is stirred for 3 days at room temperature.

The mixture is diluted with 5 ml water and 5 ml ethylacetate, separated and the organic phase is washed with sat. NH₄Cl solution and water. The organic phase is dried over sodium sulfate and evaporated. Yield: 200 mg (62%).

Example C Preparation of 1-Methyl-3-trifluoromethyl-1H-pyrazole4-carboxylic acid [2-(3-chloro-5-trifluoromethyl-pyridin-2-yl)-ethyl]-amide

132 mg (3.5 mmol) of sodium borohydrate is added in small portions to a solution of 370 mg (1.0 mmol) 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid-anhydride, 110 mg (0.5 mmol) (3-chloro-5-trifluormethyl-pyridin-2-yl)-acetonitrile and 120 mg (0.5 mmol) Nickel(II) chloride hexahydrate in 5 ml of acetonitrile at 0° C. Stirring was continued at room temperature for 4 hours.

After evaporation of the solvent, the residue is purified by column chromatography over silica-gel (eluant:hexane/ethylacetate=10:1 to 1:1). Yield: 80 mg (40%).

Examples of Biological Activity of the Compound of General Formula (I) Example 1 In Vivo Test on Alternaria brassicae (Leaf Spot of crucifers)

The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l. This suspension is then diluted with water to obtain the desired active material concentration.

Radish plants (Pernot variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-20° C., are treated at the cotyledon stage by spraying with the aqueous suspension described above.

Plants, used as controls, are treated with an aqueous solution not containing the active material.

After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Alternaria brassicae spores (40,000 spores per cm³). The spores are collected from a 12-13-day-old culture.

The contaminated radish plants are incubated for 6-7 days at about 18° C., under a humid atmosphere.

Grading is carried out 6 to 7 days after the contamination, in comparison with the control plants.

Under these conditions, good (at least 50%) to total protection is observed at a dose of 330 ppm with the following compounds: A-3, A-4, B-2, B-4, B-5, B-7, B-8, B-9, B-10, B-13, B-14, B-16, C-2, C-3, C-5, C-6, C-8, C-12, C-13, C-14, C-16, C-18, C-21, C-23, D-4, D-5, E-3, E-4, F-3, G-1, H-1, H-2, H-4, H-6, H-7, H-17, H-19, H-22, H-23, I-1, I-3, J-1, J-2, J-3, J-4, J-5, J-6, J-12, J-13, J-19, J-22, J-24, J-25, J-26, J-31, J-32, J-33, J-35, J-36, J-37, J-38, J-39, J-41, J-43, J-45, J-47, J-49, J-50, J-51, J-52, J-53, J-55, K-3, K-5, K-6, M -2, M-4, M-5, M-6, N-1, O-1, Q-1, Q-2, R-1, R-5, R-6, R-7, R-10, R-11, R-13, R-14, R-15, R-23, R-24, R-26, R-30, R-31, S-2, S-5, V-1, V-6, V-7, V-8, V-12.

Example 2 In Vivo Test on Erysiphe graminis f. sp. tritici (Wheat Powdery Mildew)

The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l. This suspension is then diluted with water to obtain the desired active material concentration.

Wheat plants (Audace variety) in starter cups, sown on 50/50 peat soil-pozzolana substrate and grown at 12° C., are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above.

Plants, used as controls, are treated with an aqueous solution not containing the active material.

After 24 hours, the plants are contaminated by dusting them with Erysiphe graminis f. sp. tritici spores, the dusting being carried out using diseased plants. Grading is carried out 7 to 14 days after the contamination, in comparison with the control plants.

Under these conditions, good (at least 50%) to total protection is observed at a dose of 330 ppm with the following compounds: A-4, B-4, B-8, C-2, C-3, C-12, D-4, F-1, H-1, H-2, H-4, H-20, I-3, J-1, J-2, J-3, J-19, J-20, J-31, J-37, J-40, J-55, J-57, J-58, J-59, J-61, K-1, M-5, M-6, R-1, R-10, R-26, R-29, V-7.

Example 3 In Vivo Test on Botrytis cinerea (Cucumber Grey Mould)

The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l. This suspension is then diluted with water to obtain the desired active material concentration.

Cucumber plants (Marketer variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-20° C., are treated at the cotyledon Z11 stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.

After 24 hours, the plants are contaminated by depositing drops of an aqueous suspension of Botrytis cinerea spores (150,000 spores per ml) on upper surface of the leaves. The spores are collected from a 15-day-old culture and are suspended in a nutrient solution composed of:

-   -   20 g/L of gelatin     -   50 g/L of cane sugar     -   2 g/L of NH4NO3     -   1 g/L of KH2PO4

The contaminated cucumber plants are settled for 5/7 days in a climatic room at 15-11° C. (day/night) and at 80% relative humidity.

Grading is carried out 5/7 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 50%) to total protection is observed at a dose of 330 ppm with the following compounds :B-7, B-8, B-13, B-14, C-3, C-12, C-13, C-14, C-15, C-16, D-4, D-5, E-4, H-1, H-2, H-4, H-7, H-9, H-22, J-1, J-2, J-3, J-19, J-31, J-32, J-33, J-34, J-35, J-37, J-39, J-43, J-44, R-1, R-10, R-23, R-24, R-26, R-31, V-1, V-8.

Example 4 In Vivo Test on Pyrenophora teres (Barley Net Blotch)

The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l. This suspension is then diluted with water to obtain the desired active material concentration.

Barley plants (Express variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 12° C., are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.

After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Pyrenophora teres spores (12,000 spores per ml). The spores are collected from a 12-day-old culture The contaminated barley plants are incubated for 24 hours at about 20° C. and at 100% relative humidity, and then for 12 days at 80% relative humidity.

Grading is carried out 12 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 50%) to total protection is observed at a dose of 330 ppm with the following compounds A-4, B-3, B-7, B-8, B-13, B-14, B-15, B-16, C-3, C-5, C-12, C-13, C-14, C-15, C-16, C-17, C-20, C-22, C-23, D-4, D-5, E-3, E-4, F-3, G-1, H-1, H-2, H-4, H-5, H-6, H-7, H-8, H-11, H-15, H-17, H-19, H-20, H-22, H-23, I-1, I-3, J-1, J-2, J-3, J-7, J-8, J-10, J-19, J-20, J-22, J-23, J-24, J-25, J-26, J-31, J-32, J-33, J-34, J-35, J-36, J-37, J-39, J-40, J-41, J-42, J-43, J-44, J-46, J-49, J-50, J-51, J-52, J-54, J-55, J-57, J-58, J-59, J-61, K-6, M-4, P-1, R-1, R-9, R-10, R-14, R-15, R-23, R-26, R-30, R-31, S-2, V-1, V-7, V-8, V-11, V-12, V-13.

Example 5 In Vivo Test on Peronospora brassicae (Cabbage Downy Mildew)

The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l. This suspension is then diluted with water to obtain the desired active material concentration.

Cabbage plants (Eminence variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-20° C., are treated at the cotyledon stage by spraying with the aqueous suspension described above.

Plants, used as controls, are treated with an aqueous solution not containing the active material.

After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Peronospora brassicae spores (50,000 spores per ml). The spores are collected from infected plant.

The contaminated cabbage plants are incubated for 5 days at 20° C., under a humid atmosphere.

Grading is carried out 5 days after the contamination, in comparison with the control plants.

Under these conditions, good (at least 50%) to total protection is observed at a dose of 330 ppm with the following compounds :B-6,B-7, J-46, J-59.

Under these conditions, the N-{1-ethylcarbanoyl-2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl}-4-chlorobenzamide, the N-{1-ethylcarbamoyl-2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl}-3-nitrobenzamide, the N-{1-ethylcarbamoyl-2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl}-2-bromobenzamide, the N-{1-methylcarbamoyl-2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl}methoxybenzamide and the N-{1-methylcarbamoyl-2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl}-4-phenylbenzamide disclosed by Patent Application WO 01/11965 (see respectively compounds 306, 307, 310, 315 and 316 in Table D) showed poor efficacy against Alternaria brassicae and Pyrenophora teres and no efficacy against Botrytis cinerea and Peronospora parasitica at 330 ppm.

Under these conditions, the N-{[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-methyl}-5-thienylacetamide disclosed by Patent Application WO 01/11965 (see compound 101 in table B) showed poor efficacy against Alternaria brassicae and no efficacy against Botrytis cinerea and Peronospora parasitica at 330 ppm. 

1. A compound of the general formula (I):

in which: X is an oxygen atom; each Y is independently selected from the group consisting of a halogen atom, a nitro group, a cyano group, a hydroxy, C1-C6-alkoxy-C1-C6-alkylcarbonyl, a carboxyl group, a C₁-C₈-alkyl, a C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₈-alkylamino, a di-C₁-C₈-alkylamino, a C₁-C₈-alkoxy, a C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₈-alkylthio, a C₁-C₆-halogenoalkylthio having 1 to 5 halogen atoms, a C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1 to 5 halogen atoms, a C₃-C₈-alkinyloxy, a C₃-C₈-halogenoalkinyloxy having 1 to 5 halogen atoms, a C₃-C₈-cycloalkyl, a C₁-C₈-alkoxycarbonyl, a C₁-C₈-alkylsulphinyl, a C₁-C₈-alkylsulphonyl, a C₁-C₈-halogenoalkylsulphinyl having 1 to 5 halogen atoms, a C₁-C₈-halogenoalkylsulphonyl having 1 to 5 halogen atoms and a C₁-C₆-alkoximino-C₁-C₆-alkyl, provided that at least one Y substituent is a C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms; R¹ is selected from the group consisting of a hydrogen atom, a cyano group, a nitro group, a formyl group, a C₁-C₆-alkyl, a C₁-C₆-alkylcarbamoyl, a C₂-C₆-alkenyl, a C₂-C₆-alkynyl, a C₁-C₆-halogenoalkyl having 1 to 7 halogen atoms, a C₁-C₆-alkoxy-C₁-C₆-alkyl, a C₁-C₆-cyanalkyl, a C₁-C₆-aminoalkyl, a C₃-C₆-cycloalkyl, a C₁-C₆-alkylcarbonyl, a C₁-C₆-halogenalkylcarbonyl having 1 to 5 halogen atoms, a C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl, a C₁-C₆-alkylsulfanyl and a C₁-C₆-halogenalkylsulfanyl having 1 to 5 halogen atoms; n is 1, 2, 3 or 4; and Het is selected from the group consisting of substituted 6-membered heterocyclic moieties selected from the group consisting of:

wherein: R⁵¹ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-akylthio, a C₁-C₄-halogenoakylthio having 1 to 5 halogen atoms or a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms; R⁵², R⁵³ and R⁵⁴ are independently selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl or a C₁-C₄-alkylsulphonyl; provided that at least one of R⁵¹, R⁵², R⁵³, and R⁵⁴ is not hydrogen;

wherein: R⁵⁵ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₅-alkylthio, a C₂-C₅-alkenylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a phenyloxy optionally substituted by a halogen atom or a C₁-C₄-alkyl, or a phenylthio optionally substituted by a halogen atom or a C₁-C₄-alkyl; R⁵⁶, R⁵⁷ and R⁵⁸ are independently selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl, a C₁-C₄-alkylsulphonyl or a N-morpholine optionally substituted by a halogen atom or a C₁-C₄-alkyl, or a thienyl optionally substituted by a halogen atom or a C₁-C₄-alkyl; provided that at least one of R⁵⁵, R⁵⁶, R⁵⁷, and R⁵⁸ is not hydrogen; and

wherein R⁵⁹, R⁶⁰, R⁶¹ and R⁶² are independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl or a C₁-C₄-alkylsulphonyl; provided that at least one of R⁵⁹, R⁶⁰, R⁶¹, and R⁶² is not hydrogen; Het being linked by a carbon atom, as indicated.
 2. The compound of claim 1 wherein n is 1 or
 2. 3. The compound of claim 2 wherein n is
 2. 4. The compound of claim 1 wherein there is at least one Y substituent that is selected from the group consisting of a halogen atom, a C₁-C₈-alkyl, and a C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl.
 5. The compound of claim 1 wherein at least one Y substituent is —CF₃.
 6. The compound of claim 1 wherein the 2-pyridyl group of the (pyridin-2-yl)-ethyl moiety is substituted in the 3- and/or in the 5-position.
 7. The compound of claim 5 wherein the 2-pyridyl group of the (pyridin-2-yl)-ethyl moiety is substituted in the 5-position by —CF₃.
 8. A fungicidal composition comprising an effective amount of a compound according to claim 1, and an agriculturally acceptable support.
 9. The fungicidal composition of claim 8 further comprising a surfactant.
 10. The fungicidal composition of claim 8, comprising from 0.05% to 99% by weight of the compound of formula I.
 11. The compound of claim 6 wherein the 2-pyridyl group of the (pyridin-2-yl)-ethyl moiety is substituted in the 5-position by —CF₃.
 12. The fungicidal composition of claim 9, comprising from 0.05% to 99% by weight of the compound of formula I.
 13. A method for combating and/or controlling phytopathogenic fungi selected from the group consisting of Alternaria brassicae and Pyrenophora teres comprising applying an effective and non-phytotoxic amount of a compound of the general formula (I):

in which: X is an oxygen atom; each Y is independently selected from the group consisting of a halogen atom, a nitro group, a cyano group, a hydroxy, a C1-C6-alkoxy-C1-C6-alkylcarbonyl, a carboxyl group, a C₁-C₈-alkyl, a C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₈-alkylamino, a di-C₁-C₈-alkylamino, a C₁-C₈-alkoxy, a C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₈-alkylthio, a C₁-C₆-halogenoalkylthio having 1 to 5 halogen atoms, a C₂-C₈-alkenyloxy, a C₂-C₈-halogenoalkenyloxy having 1 to 5 halogen atoms, a C₃-C₈-alkinyloxy, a C₃-C₈-halogenoalkinyloxy having 1 to 5 halogen atoms, a C₃-C₈-cycloalkyl, a C₁-C₈-alkoxycarbonyl, a C₁-C₈-alkylsulphinyl, a C₁-C₈-alkylsulphonyl, a C₁-C₈-halogenoalkylsulphinyl having 1 to 5 halogen atoms, a C₁-C₈-halogenoalkylsulphonyl having 1 to 5 halogen atoms and a C₁-C₆-alkoximino-C₁-C₆-alkyl, provided that at least one Y substituent is a C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms; R¹ is selected from the group consisting of a hydrogen atom, a cyano group, a nitro group, a formyl group, a C₁-C₆-alkyl, a C₁-C₆-alkylcarbamoyl, a C₂-C₆-alkenyl, a C₂-C₆-alkynyl, a C₁-C₆-halogenoalkyl having 1 to 7 halogen atoms, a C₁-C₆-alkoxy-C₁-C₆-alkyl, a C₁-C₆-cyanalkyl, a C₁-C₆-aminoalkyl, a C₃-C₆-cycloalkyl, a C₁-C₆-alkylcarbonyl, a C₁-C₆-halogenalkylcarbonyl having 1 to 5 halogen atoms, a C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl, a C₁-C₆-alkylsulfanyl and a C₁-C₆-halogenalkylsulfanyl having 1 to 5 halogen atoms; n is 1, 2, 3 or 4; and Het is selected from the group consisting of substituted 6-membered heterocyclic moieties selected from the group consisting of:

wherein: R⁵¹ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-akylthio, a C₁-C₄-halogenoakylthio having 1 to 5 halogen atoms or a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms; R⁵², R⁵³ and R⁵⁴ are independently selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl or a C₁-C₄-alkylsulphonyl; provided that at least one of R⁵¹, R⁵², R⁵³, and R⁵⁴ is not hydrogen;

wherein: R⁵⁵ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₅-alkylthio, a C₂-C₅-alkenylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a phenyloxy optionally substituted by a halogen atom or a C₁-C₄-alkyl, or a phenylthio optionally substituted by a halogen atom or a C₁-C₄-alkyl; R⁵⁶, R⁵⁷ and R⁵⁸ are independently selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₁-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl, a C₁-C₄-alkylsulphonyl or a N-morpholine optionally substituted by a halogen atom or a C₁-C₄-alkyl, or a thienyl optionally substituted by a halogen atom or a C₁-C₄-alkyl; provided that at least one of R⁵⁵, R⁵⁶, R⁵⁷, and R⁵⁸ is not hydrogen; and

wherein R⁵⁹, R⁶⁰, R⁶¹ and R⁶² are independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl or a C₁-C₄-alkylsulphonyl; provided that at least one of R⁵⁹, R⁶⁰, R⁶¹,and R⁶² is not hydrogen; Het being linked by a carbon atom, as indicated; to plant seeds or to the plant leaves and/or to fruits of plants or to soil in which plants are growing or in which the plants are desired to grow.
 14. The method of claim 13 wherein Het represents a heterocycle of the general formula (XXII)

in which: R⁵¹ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms and a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms; and R⁵², R⁵³ and R⁵⁴, are independently selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl and a C₁-C₄-alkylsulphonyl.
 15. The method of claim 13 wherein Het represents a heterocycle of the general formula (XXIII)

in which: R⁵⁵ is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C5-alkylthio, a C₂-C5-alkenylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a phenyloxy optionally substituted by a halogen atom or a C₁-C₄-alkyl, and a phenylthio optionally substituted by a halogen atom or a C₁-C₄-alkyl; R⁵⁶, R⁵⁷ and R⁵⁸ are independently selected form the group consisting of a hydrogen atom, a halogen atom, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkyl-sulphinyl, a C₁-C₄-alkylsulphonyl, a N-morpholine optionally substituted by a halogen atom or a C₁-C₄-alkyl, and a thienyl optionally substituted by a halogen atom or a C₁-C₄-alkyl.
 16. The method of claim 13 wherein Het represents a heterocycle of the general formula (XXIV)

in which R^(59, R) ⁶⁰, R⁶¹ and R⁶² are independently selected from the group consisting of a halogen atom, a hydroxy group, a cyano group, a C₁-C₄-alkyl, a C₁-C₄-halogenoalkyl having 1 to 5 halogen atoms, a C₁-C₄-alkoxy, a C₁-C₄-alkylthio, a C₁-C₄-halogenoalkylthio having 1 to 5 halogen atoms, a C₁-C₄-halogenoalkoxy having 1 to 5 halogen atoms, a C₁-C₄-alkylsulphinyl and a C₁-C₄-alkylsulphonyl.
 17. The method of claim 13 wherein n is 1 or
 2. 18. The method of claim 17 wherein n is
 2. 19. The method of claim 13 wherein there is at least one Y substituent that is selected from the group consisting of a halogen atom, a C₁-C₈-alkyl, and a C₁-C₆-alkoxy-C₁-C₆-alkylcarbonyl.
 20. The method of claim 13 wherein at least one Y substituent is —CF₃.
 21. The method of claim 13 wherein the 2-pyridyl group of the (pyridin-2-yl)-ethyl moiety is substituted in the 3- and/or in the 5-position.
 22. The method of claim 20 wherein the 2-pyridyl group of the (pyridin-2-yl)-ethyl moiety is substituted in the 5-position by —CF₃.
 23. The method of claim 21 wherein the 2-pyridyl group of the (pyridin-2-yl )-ethyl moiety is substituted in the 5-position by —CF₃. 